JPH0433772B2 - - Google Patents

Description

[Detailed description of the invention]

(Technical Field) The present invention relates to a novel diethynylbenzene derivative useful as a resist material, an organic semiconductor, an electronic material such as a conductive material, and the like. (Industrial Application Field) Diethynylbenzene compounds, in which two ethynyl groups are directly bonded to the benzene ring, generally have γ
It is highly sensitive to energy irradiation such as beams, electron beams, , X-ray resists, patterning materials such as photoresists, or heat-sensitive materials. In addition, the polymer given by the energy irradiation becomes a conjugated polymer in which the C≡C triple bond opens to form a conjugated double bond, so it is an organic semiconductor,
It can also be used as a conductive electronic material. Further, the diethynylbenzene derivative of the present invention can be used to produce an amphipathic compound by, for example, oxidizing the vinyl group at the end of the molecule to convert it into a carboxylic acid. A hydrophobic structural part such as a long chain structure consisting of an appropriate number of methylene groups in the molecule,
Amphipathic compounds that have both hydrophilic structural moieties such as amino groups, hydroxyl groups, and carboxyl groups form a monomolecular film on the water surface. This monomolecular film was prepared using the Langmuir Blosget method (hereinafter referred to as “LB”).
(The film produced by this method is also called the "LB film.") It is possible to accumulate on a suitable substrate and form a highly oriented molecular cumulative film.In particular, diethinyl in the molecules can be accumulated on a suitable substrate. LB films made of amphiphilic molecules with structural moieties such as benzene can be applied to pattern-forming materials such as resists, electronic materials such as organic semiconductors and conductive materials, and optoelectronic materials such as nonlinear optical materials. ,
Very useful in industry. (Prior art and problems) Until now, diethynylbenzene

[Formula] or general formula

[Formula] (n is 1 a compound represented by (an integer greater than or equal to 4), and

Compounds like [Formula] are already known [JK Crandall et al.
Journal of American Chemical Society, 97
(24), 7171-2 (1975); EARunova et al., Vestn.
Mosk.Univ., Ser.2: Khim., 24(3), 299-300
(1983) etc.]. Diethynylbenzene compounds are resistant to gamma rays, electron beams,
It is sensitive to energy irradiation such as ultraviolet rays, visible light, and infrared rays (heat), but its small molecular weight makes it difficult to produce high-quality thin films, and its sublimation property makes it difficult to handle under reduced pressure. It was hot. The application of the LB method to the production of thin films of compounds with a diethynylbenzene structure is considered, but no diethynylbenzene compounds with the amphiphilic properties necessary for the production of LB films are known, nor are the raw materials for their production known. . (Means for Solving the Problems) In view of these problems, the present inventors developed a diethynylbenzene compound that can be made into a thin film, is non-sublimable, and is applicable to the LB technology. As a result of intensive studies to obtain a diethynylbenzene compound which is a raw material for producing a medium compound, the diethynylbenzene derivative of the present invention was finally obtained. That is, the present invention provides a novel diethynyl compound represented by the general formula below, which has a diethynylbenzene structure and a methylene chain in the molecule, a vinyl group at one molecular end, and a hydrogen or alkylsilyl group at the other molecular end. Regarding benzene derivatives. [R in the formula is hydrogen or -SiX ₁ X ₂ X ₃ , X ₁ , X ₂ ,
X ₃ is each independently hydrogen or an alkyl group having 1 to 7 carbon atoms (except when X ₁ , X ₂ , and X ₃ are all hydrogen), and n is an integer of 9 or more and 21 or less. ] Due to its molecular structural characteristics, the diethynylbenzene derivative of the present invention has C-H stretching vibrations of the benzene ring and vinyl group, C-H stretching vibrations of the methylene group, and C≡C stretching vibrations of 3000 to 3000, respectively, in the IR absorption spectrum. 3080cm ^-1 , 2850～2960cm ^-1 , 2010～
Observed at 2260cm ^-1 I. In addition, absorption peculiar to the benzene ring is observed near 1600 cm ^-1 and 1500 cm ^-1 , and C-H out-of-plane bending vibration of the benzene ring is observed between 690 and 860 cm ^-1 . In addition, in the ¹ H-NMR spectrum, the = _CH2 and -CH=C protons of the benzene ring and vinyl group are 6.9 to 7.8 ppm, 3.9 to 6.4 ppm, and 3.9 to 6.4 ppm, respectively.
5.3 to 7.3 ppm, and the protrons of methylene groups adjacent to C≡C, methylene groups adjacent to vinyl groups, and other methylene groups are 2.2 to 7.3 ppm, respectively.
Observed at 2.5ppm, 1.8~2.2ppm, and 0.6~1.9ppm. In addition, IR absorption due to the structure of substituent R, ¹
H-NMR signals are also observed in each spectrum. In the general formula of the diethynylbenzene derivative of _the present invention, the substituent R is hydrogen or -SiX ₁ X ₂ X ₃ , and examples of -SiX ₁ X ₂ group, tributylsilyl group, triheptylsilyl group, diethylsilyl group, etc. Furthermore, the substitution mode of the two ethynyl groups on the benzene ring may be any of ortho, meta, and para. The diethynylbenzene derivative of the present invention is solid at 15°C and is soluble in solvents such as acetone, methyl ethyl ketone, ethanol, ethyl acetate, chloroform, benzene, and hexane. Next, an example of the method for synthesizing the diethynylbenzene derivative of the present invention will be explained. First, a scheme of the synthesis reaction is shown below. First, using diethynylbenzene 1 as one of the starting materials, two ethynyl groups of diethynylbenzene are metal-halogenated by the Grignard method to obtain compound 2. This compound 2 is converted into X ₁ X ₂ X ₃ SiCl (X ₁ ,
X ₂ and X ₃ are each independently hydrogen or have a carbon number of 1 to
7 alkyl group, X ₁ , X ₂ , X ₃
are not all hydrogen at the same time),
Bisalkylsilylated ethynylbenzene 3 Synthesize. On the other hand, alkenyl alcohol 4 CH ₂ = CH- (CH ₂ ) _o -OH (where n is 9
21 or less) as another starting material and reacted with tosyl chloride to form alkenyl tosylate 5 CH ₂ =CH-(CH ₂ ) _o -OT _s (where n is an integer of 9 or more and 21 or less, T _s is a tosyl group)
Synthesize. By desilylating one of the alkylsilyl groups of the bisalkylsilylated ethynylbenzene 3 and alkenyl tosylate 5 described above using methyllithium or the like to obtain an organometallic compound 6, and reacting it with the alkenyl tosylate 5, the present invention can be obtained. R _of the invention is -SiX ₁ X ₂ X _{3 ( X 1} ,
A diethynylbenzene derivative 7 can be synthesized in which X ₂ and X ₃ are not all hydrogen at the same time. Moreover, the diethynylbenzene derivative of the present invention in which R is hydrogen, R is an alkylsilyl group, -SiX ₁
The _above derivative _of X ₂ It can be obtained by desilylation. However, when using KF as a desilylating agent, it is preferable to use it together with a crown compound. Although an example of the method for producing the diethynylbenzene derivative of the present invention has been described above, the production method is not limited thereto. (Effects of the Invention) The diethynylbenzene derivative of the present invention is capable of forming a thin film and is non-sublimable. Therefore, the diethynylbenzene derivative of the present invention can be used as a pattern-forming material or a heat-sensitive material by forming a thin film, and can be applied as an electronic material such as an organic semiconductor or a conductive material by forming a polymer. It can be used for. Furthermore, the diethynylbenzene derivative of the present invention is
For example, an amphipathic compound can be produced by converting the vinyl group at the end of the molecule into a carboxyl group through an oxidation reaction such as ozone oxidation. It can be applied to forming materials, electronic materials such as conductive materials, or optoelectronic materials such as nonlinear optical materials. The present invention will be explained in more detail with reference to Examples below. Example 1 0.2 mol of p-diethynylbenzene was dissolved in 350 ml of sufficiently dehydrated tetrahydrofuran and heated to -78°C.
Then, 0.4 mol of ethylmagnesium bromide was added and reacted at 25°C for 1 hour. Next, this reaction solution was cooled again to -78℃, and trimethylsilyl chloride was added.
0.4 mol was added and reacted at 25°C for 2 hours to obtain bis-(trimethylsilylethynyl)-benzene. Additionally, 0.04 mol of ω-heptadecenyl alcohol was dissolved in 30 ml of pyridine, and while the reaction vessel was immersed in an ice bath, 0.045 mol of trienesulfonyl chloride (tosyl chloride) was added and reacted at 15°C for 24 hours. Got the rate. Next, bis-(trimethylsilyl)-benzene 0.01
mol was dissolved in 60 ml of sufficiently dehydrated tetrahydrofuran, 0.01 mol of methyllithium was added at -78°C, and the mixture was reacted at 25°C for 2 hours. The reaction solution was cooled again to -78°C, and hexamethylphosphoramide 35
ml and 0.01 mol of heptadecenyl tosylate were added and reacted at 25°C for 1 hour. To this reaction solution were added 250 ml of a saturated aqueous solution of sodium bicarbonate and 180 ml of diethyl ether, and the mixture was thoroughly shaken to extract the product into the ether phase. The ether phase was washed with a saturated aqueous sodium chloride solution and then dehydrated with magnesium sulfate. This ether solution was concentrated to give white yellow crystals. Purification by GPC yielded 1-(18-nonadecen-1-ynyl)-4-(trimethylsilylethynyl)-benzene. 40 mmol of white crystals were obtained. The IR spectrum and ¹ H-NMR spectrum of this crystal were measured to investigate its structure.
The IR spectrum obtained by the KBr tablet method is shown in Figure 1. As can be seen from this spectrum, the C-H stretching vibration of the benzene ring and the vinyl group at the end of the molecule is 3020 to 3080 cm ^-1 , and the C-H stretching vibration of the methyler group is 2850 to 2920 cm ^-1. The vibration
At 2960cm ^-1 , the C≡C stretching vibration of -C≡C- is 2150
In cm ^-1 , the C=C stretching vibration of vinyl group is 1640 cm
^-1 , the skeletal vibration of the benzene ring was observed at 1490 cm ^-1 and the C-H out-of-plane bending vibration of the benzene ring was observed at 840 cm ^-1 . In addition, 1400cm derived from the methyl group of Si- _CH3
^-1 , 1240cm ^-1 , 860cm ^-1 K derived from Si-C stretching vibration
Absorption was observed. The ¹ H-NMR spectrum measured with a deuterated chloroform solution is shown in Figure 2. As you can see from this spectrum, the benzene ring proton is 7.44ppm
, the =CH- proton of the vinyl group is 5.9 ppm,
The =CH ₂ proton of vinyl is 5.2ppm, -C≡C
The proton of the methylene group adjacent to the − group is 2.4 ppm
, the proton of the methylene group adjacent to the vinyl group is
2.0 ppm, and 0.8 protons of other methylene groups
At ~1.8ppm, protons of trimethylsilyl group
0.04ppm respectively 4:1:2:2:2:26:9
It was observed with a signal integration degree ratio of . By converting the vinyl group into a carboxyl group by ozone oxidation of the compound, an amphiphilic diethynylbenzene derivative carboxylic acid could be synthesized. Using the thus obtained diethynylbenzene derivative carboxylic acid, a 59-layer cumulative film was fabricated on a SiO ₂ -coated silicon wafer by the LB method. this
Cover the LB film with a mask for photoresist and apply 100W
After 1 minute exposure with a low pressure mercury lamp, 1 minute exposure with ethanol
As a result of developing for a minute, only the unexposed areas were dissolved in ethanol, and a negative pattern could be formed. Example 2 1-(18-nonadecene-1 obtained by the method of Example 1)
-ynyl)-4-(trimethylsilylethynyl)-
In a solution of 20 mmol of benzene in tetrahydrofuran,
A solution of (C ₄ H ₉ ) ₄ NF in tetrahydrofuran, (C ₄
H ₉ ) ₄ NF was added in an amount of 25 equivalents of the trimethylsilyl group, and the mixture was stirred at 25° C. for 20 hours to carry out a desilylation reaction. Next, a small amount of water was added to this reaction solution, and after thorough shaking, the ether layer was separated. Repeat this operation to combine the ether layers and concentrate to obtain 1-ethynyl-4-(18nonadecen-1-ynyl)-benzene. 30 mmol of white crystals were obtained. From the IR spectrum,
C-H stretching vibration of benzene ring and vinyl group is 3020
At ~3080cm ^-1 , the C-H stretching vibration of the methylene group
At 28502920 cm ^-1 , the C-H stretching vibration and C≡C stretching vibration of the ethynyl group are 3300 cm ^-1 and 2150 cm ^-1, respectively.
In addition, the C=C stretching vibration of the vinyl group was observed at 1640 cm ^-1 , and the skeletal vibration and C-H out-of-plane bending vibration of the benzene ring were observed at 1490 cm ^-1 and 840 cm ^-1 I, respectively. The ¹ H-NMR spectrum is shown in Figure 3. As can be seen from this spectrum, the benzene ring proton is at 7.44 ppm, the vinyl group's =CH- proton and = _CH2 proton are each at 5.0 ppm,
At 5.2ppm, the proton of the ethynyl group at the end of the molecule
3.1 ppm, protons of the methylene group adjacent to -C≡C- are 2.4 ppm, protons of the methylene group adjacent to the vinyl group are 2.0 ppm, protons of other methylene groups are 0.8 to 1.8 ppm, and 4 ppm, respectively. :
It was observed with a signal integrated intensity ratio of 1:2:1:2:2:26. By converting the vinyl group into a carboxyl group by ozone oxidation of the compound, an amphiphilic diethynylbenzene derivative carboxylic acid could be synthesized. Using the thus obtained diethynylbenzene derivative carboxylic acid, a 59-layer cumulative film was fabricated on a SiO ₂ -coated silicon wafer by the LB method. this
Cover the LB film with a photoresist mask and apply 100W
After 1 minute exposure with a low pressure mercury lamp, 1 minute exposure with ethanol
As a result of developing for a minute, only the unexposed areas were dissolved in ethanol, and a negative pattern could be formed. Example 3 A similar reaction was carried out in Example 1 using ω-undecylenyl alcohol instead of ω-heptadecenyl alcohol, and first 1-(12-tridecen-1-ynyl)-4-trimethylsilylethynyl ) - benzene 46 mmol was obtained. This compound was used in Example 2 instead of 1-(18-nonadecen-1-ynyl)-4-(trimethylsilylethynyl)-benzene, and 1-ethynyl-4-(12-tridecen-
1-ynyl)-benzene Obtained 34m mol. From the IR spectrum, the C-H stretching vibration of the benzene ring and vinyl group is 3020 to 3080 cm
^-1 , the C-H stretching vibration of the methylene group is 28502920cm
^-1 , the C-H stretching vibration and C≡C stretching vibration of the ethynyl group are at 3300 cm ^-1 and 2150 cm ^-1 , respectively, the C≡C stretching vibration of the vinyl group is at 1640 cm ^-1 , the skeletal vibration of the benzene ring, and the C -H out-of-plane bending vibration is 1490 each
cm ^-1 , observed at 840 cm ^-1 . From ^{the 1} H-NMR spectrum, the benzene ring proton is 7.44 ppm, the =CH- proton and = _CH2 proton of the vinyl group are 5.9 ppm and 5.2 ppm, respectively, and the proton of the ethynyl group at the end of the molecule is 3.1 ppm. , the proton of the methylene group adjacent to -C≡C- is 2.4 ppm, and the proton of the methylene group adjacent to the vinyl group is 2.0 ppm.
In addition, the protons of other methylene groups are 0.8~
1.8ppm, respectively 4:1:2:1:2:2:
A signal integrated intensity ratio of 14 was observed. By converting the vinyl group into a carboxyl group by ozone oxidation of the compound, an amphiphilic diethynylbenzene derivative carboxylic acid could be synthesized. Using the diethynylbenzene derivative carboxylic acid thus obtained, a 59-layer cumulative film was fabricated on a SiO ₂ -coated silicon wafer by the LB method. this
Cover the photoresist mask with LB film and apply 100w
After 1 minute exposure with a low pressure mercury lamp, 1 minute exposure with ethanol
As a result of developing for a minute, only the unexposed areas were dissolved in ethanol, and a negative pattern could be formed. Example 4 The same reaction as in Example 1 was carried out using chlorotriethylsilane instead of trimethylsilyl chloride to obtain bis-(triethylsilylethynyl)-benzene. A similar reaction was carried out in Example 1 using this compound in place of bis-(trimethylsilylethynyl)-benzene, and 1-
(18-cinadecen-1-ynyl)-4-(triethylsilylethynyl)-benzene white crystal 38m
I got mol. The C-H stretching vibration of the benzene ring and the vinyl group at the end of the molecule was determined from the IR spectrum obtained by the KBr tablet method.
At 3020 to 3080 cm ^-1 , the cC-H stretching vibration of the methylene group is at 28502920 cm ^-1 , the C-H stretching vibration of the methyl group is at 2960 cm ^-1 , and the C≡C stretching vibration of -C≡C-
At 1640cm ^-1 , the C=C stretching vibration of the vinyl group is 1640cm
^-1 , the skeletal vibration of the benzene ring was observed at 1490 cm ^-1 and the C-H out-of-plane bending vibration of the benzene ring was observed at 840 cm ^-1 . In addition, 1408 derived from the methylene group of Si-CH ₂ CH ₃
cm ^-1 , 1234cm ^-1 , 860cm ^-1 derived from Si-C stretching vibration
absorption was observed. In addition, from ^{the 1H} -NMR spectrum, the proton of the benzene ring is 7.44 ppm, the proton of =CH- of the vinyl group is 5.9 ppm, the proton of = _CH2 of the vinyl group is 5.2 ppm, and the proton of the -C≡C- group is The proton of the adjacent methylene group is 2.4 ppm,
The proton of the methylene group adjacent to the vinyl group
2.0 ppm, and 0.8 protons of other methylene groups
~1.8ppm, the protons of the methyl group and methylene group of the triethylsilyl group are each 0.9ppm,
0.6ppm, respectively 4:1:2:2:2:26:
Observed with a signal integrated intensity ratio of 9:6. By converting the vinyl group into a carboxyl group by ozone oxidation of the compound, an amphiphilic diethynylbenzene derivative carboxylic acid could be synthesized. Using the thus obtained diethynylbenzene derivative carboxylic acid, a 59-layer cumulative film was fabricated on a SiO ₂ -coated silicon wafer by the LB method. this
Cover the LB film with a photoresist mask and apply 100W
After 1 minute exposure with a low pressure mercury lamp, 1 minute exposure with ethanol
As a result of developing for a minute, only the unexposed areas were dissolved in ethanol, and a negative pattern could be formed. Example 5 The same reaction as in Example 1 was carried out using chlorotriheptylsilane instead of trimethylsilyl chloride to obtain bis-(triheptylsilylethynyl)-benzene. This compound was used in Example 1 as bis-(trimethylsilylethynyl)
- Carry out a similar reaction using instead of benzene,
White crystals of 1-(18-nonadecen-1-ynyl)-4-(triheptylcycluethynyl)-benzene
24 mmol was obtained. By converting the vinyl group into a carboxyl group by ozone oxidation of the compound, an amphipathic diethynylbenzene derivative carboxylic acid can be synthesized. Using the thus obtained diethynylbenzene derivative carboxylic acid, a 39-layer cumulative film was fabricated on a SiO ₂ -coated silicon wafer by the LB method. this
Cover the LB film with a photoresist mask and apply 100W
After 1 minute exposure with a low pressure mercury lamp, 1 minute exposure with ethanol
As a result of developing for a minute, only the unexposed areas were dissolved in ethanol, and a negative pattern could be formed. Example 6 First, ω-tricosenyl alcohol CH ₂ =CH-(CH ₂ ) ₂₀ -COOH is reduced with lithium aluminum hydride to form ω-tricosenyl alcohol CH ₂ =CH-(CH ₂ ) ₂₁ -OH I got it.
A similar reaction was carried out using this ω-tricocenyl alcohol in place of ω-heptadecenyl alcohol in Example 1. First, 1-(24-pentacocen-1-ynyl)-4-trimethylsilylethynyl)- benzene 40mmol was obtained. This compound was used in Example 2 as 1-(18-nonadecen-1-ynyl)-4-
A similar reaction was carried out using (trimethylsilylethynyl)-benzene instead of 1-ethynyl-4-
(24-pentacocen-1-ynyl)-benzene 15mmol was obtained. By oxidizing the compound with ozone and converting the vinyl group into a carboxyl group,
We were able to synthesize amphiphilic diethynylbenzene derivative carboxylic acid. Using the thus obtained diethynylbenzene derivative carboxylic acid, a 59-layer cumulative film was fabricated on a SiO ₂ -coated silicon wafer by the LB method. this
Cover the LB film with a photoresist mask and apply 100W
After 1 minute exposure with a low pressure mercury lamp, 1 minute exposure with ethanol
As a result of developing for a minute, only the unexposed areas were dissolved in ethanol, and a negative pattern could be formed.

[Brief explanation of drawings]

Figure 1 shows 1-(18-
IR spectrum of nonadecen-1-ynyl)-4-(tritomethylsilylethynyl)-benzene, 2nd
The figure shows the ¹ H-NMR spectrum of 1-(18-nonadecen-1-ynyl)-4-(trimethylsilylethynyl)-benzene in deuterated chloroform, and Figure 3 shows the 1-ethynyl-4-( 18
-nonadecen-1-ynyl)-benzene ^1H-
This is an NMR spectrum.

Claims (1)

[Claims] 1. General formula [R in the formula is hydrogen or -SiX ₁ X ₂ X ₃ , X ₁ ,
X ₂ and X ₃ are each independently hydrogen or have a carbon number of 1 to
7 alkyl group (excluding cases where X ₁ , X ₂ , and X ₃ are all hydrogen), and n is an integer of 9 or more and 21 or less]